CN102956891A - Preparation method of lithium ion battery cathode active material Fe3O4/C, cathode and lithium ion battery - Google Patents
Preparation method of lithium ion battery cathode active material Fe3O4/C, cathode and lithium ion battery Download PDFInfo
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Abstract
The invention provides a preparation method of a lithium ion battery cathode active material Fe3O4/C, which comprises the following steps: S1, adding a surfactant and a precipitating agent into an organic solvent, mixing to obtain a solution A; S2, dissolving soluble trivalent metal ferric salt in water to obtain a solution B; S3, adding the solution B into the solution A, maintaining a temperature of 100-200 DEG C for 10-15 hours in a reaction vessel, then naturally cooling to obtain a precursor; S4, removing impurities on the precursor surface, drying, heating in inert atmosphere with a speed of 5-15 DEG C/min to 300-800 DEG C, performing heat preservation for 0.5-2 hours, naturally cooling to obtain the active material, wherein the precipitating agent is a substance capable of forming precipitates with iron ions. The invention also provides a cathode of the active material, and a lithium ion battery. The cathode active material obtained by the preparation method of the invention can be used as a battery cathode, and has quite high capacity and good cycle performance.
Description
Technical field
The invention belongs to the lithium ion battery field, relate in particular to preparation method, negative pole and the lithium ion battery of lithium ion battery negative pole active materials.
Background technology
Lithium ion battery has the advantages such as voltage is high, specific energy is large, security performance is good.The negative active core-shell material of commercial lithium-ion batteries mainly is graphite at present, and in the doff lithium process, the change in volume of graphite is little, therefore has preferably cycle performance.Graphite passes through LiC
6The reversible storage of compound Li
+, its Theoretical Mass specific capacity only has 372 mAh/g.Compare with graphite cathode, the iron-based negative active core-shell material has higher specific capacity, such as Fe
3O
4Theoretical capacity up to 928mAh/g.But because variation and dynamic (dynamical) restriction of active material volume in the metallic iron cyclic process, cause easily that electrode peels off, efflorescence and cause capacity seriously to be decayed, greatly reduce cyclicity.
In order to improve the cyclicity of battery, in conjunction with the advantage of the high power capacity of graphite stability and good cycle, iron, graphite and iron are made composite material in the prior art.Prepare at present Fe
3O
4The method of/C compound mainly is to synthesize first Fe
3O
4, FeOOH or Fe
2O
3, then being immersed in the organic carbon source, high-temperature calcination obtains Fe under inert atmosphere at last
3O
4/ C compound.
But, the negative active core-shell material that adopts method of the prior art to prepare, Fe
3O
4The capacity of the battery that/C composite material is made and cycle performance are still relatively poor.
Summary of the invention
The Fe that the present invention prepares for solving prior art
3O
4/ C is as capacity and the relatively poor technical problem of cycle performance of lithium ion battery negative pole active materials, thereby preparation method and lithium ion battery negative and the lithium ion battery of the lithium ion battery negative pole active materials of a kind of capacity and good cycle are provided.
The invention provides a kind of lithium ion battery anode active material Fe
3O
4The preparation method of/C, the method may further comprise the steps:
S1, surfactant, precipitation reagent joined be mixed into solution A in the organic solvent;
S2, with solvable trivalent metal iron salt dissolved wiring solution-forming B in water;
S3, solution B slowly is added in the solution A, then changes in the reactor, naturally cool off after 10-15 hour 100-200 ℃ of insulation, obtain presoma;
S4, remove the impurity that remains in the presoma surface, dry after under inert atmosphere, with 5-15 ℃ of min
-1Speed be warming up to 300-800 ℃ of insulation 0.5-2 hour, naturally lower the temperature, obtain negative active core-shell material;
Wherein precipitation reagent is the material that can form with iron ion precipitation.
The present invention also provides a kind of lithium ion battery negative material, and described negative material comprises negative active core-shell material, binding agent and conductive agent, and described negative active core-shell material is the negative active core-shell material that method of the present invention prepares.
The present invention also provides a kind of lithium ion battery, comprises housing, is in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Described pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Described positive plate comprises positive collector and is coated in positive electrode on the positive collector; Described negative plate comprises negative collector and is coated in the negative material of bearing on the collector; Wherein, described negative material is negative material of the present invention.
Among the preparation method of the present invention; surfactant can be coated on uniformly ferrous metal sedimentary around; after reacting under high pressure in the process reactor and 100-200 ℃ the temperature; surfactant is carbonization under high pressure; the ferrous metal sediment also resolved into ferriferous oxide, the carbon of generation be coated on uniformly iron oxide around, then under inert gas shielding, carry out reduction reaction; obtain negative active core-shell material of the present invention, the carbon that obtains according to the method is coated on Fe uniformly
3O
4Around/the C, can improve Fe
3O
4The conductivity of/C and the volumetric expansion of alleviation in charge and discharge process, capacity and the cycle performance of raising cell negative electrode material.
Description of drawings
Fig. 1 is the XRD figure of sample a1 and b1, b2;
Fig. 2 is the scanning electron microscope (SEM) photograph of the sample a2 among the embodiment 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of the sample b2 among the embodiment 2.
Embodiment
The invention provides a kind of lithium ion battery anode active material Fe
3O
4The preparation method of/C, the method may further comprise the steps:
S1, surfactant, precipitation reagent joined be mixed into solution A in the organic solvent;
S2, with solvable trivalent metal iron salt dissolved wiring solution-forming B in water;
S3, solution B slowly is added in the solution A, then changes in the reactor, naturally cool off after 10-15 hour 100-200 ℃ of insulation, obtain presoma;
S4, remove the impurity that remains in the presoma surface, dry after under inert atmosphere, with 5-15 ℃ of min
-1Speed be warming up to 300-800 ℃ of insulation 0.5-2 hour, naturally lower the temperature, obtain negative active core-shell material;
Wherein precipitation reagent is the material that can form with iron ion precipitation.
In the method for the present invention, the negative electrode active material that precursor obtains after 300 ℃ of insulations contains a small amount of α-Fe
2O
3, α-Fe
2O
3Performance impact to active material of the present invention is less, but for the performance that makes active material of the present invention is more superior, preferably, the intensification temperature among the step S4 is 500-800 ℃.
The method that described method of removing the impurity that remains in the presoma surface is commonly used for those skilled in the art, the present invention can remove the impurity on presoma surface twice with ethanol and deionized water supersound washing respectively.
According to preparation method provided by the present invention, preferably, described surfactant is that the carbon number of the carbochain between hydrophilic radical and the lipophilic group is the surfactant of 3-18.Carbon chain lengths will descend above 18 the solubility of surfactant in water, the carrying out of impact reaction; And carbon number is less than 3 surfactant, and the volatility of solution is just strong especially, and for example ethanol is unfavorable for operation, and especially in the preparation process, general liquid feeding mode all is to drip, and process is longer.
According to preparation method provided by the present invention, described surfactant can be this area various surfactants commonly used, in order to make lipophile and hydrophily more balanced, preferably, described surfactant is oleic acid, at least a in acetonitrile, salicylic acid, diglycol, glycerine, glucose, sucrose and the sodium cetanesulfonate.Oleic acid more preferably, because the oleic acid preparation is simple, cheap and have that lipophile and hydrophily are harmonious preferably.
According to preparation method provided by the present invention, preferably, described precipitation reagent is soluble hydroxide or ammoniacal liquor.NaOH more preferably.
According to preparation method provided by the present invention, preferably, described soluble metal molysite is FeCl
36H
2O, Fe (NO)
3And Fe
2(SO4)
3In at least a.
According to preparation method provided by the present invention, preferably, what described organic solvent can be in ethanol, acetone, acetic acid, ethylene glycol, chloroform, oxolane and the naphthalene is at least a.
According to preparation method provided by the present invention, preferably, the mass ratio of described surfactant, precipitation reagent and slaine is 1:0.25-25:0.1-15.More preferably, the mass ratio of described surfactant, precipitation reagent and slaine is 1:1-3.125:0.5-2.5.
According to preparation method provided by the present invention, preferably, described method stirs its mixture after also being included in and slowly being added drop-wise to solution B in the solution A, and the time of described stirring is 2-5 hour.
According to preparation method provided by the present invention, preferably, the temperature of the drying among the described step S4 is 60-100 ℃.
According to preparation method provided by the present invention, preferably, described inert atmosphere is helium, neon, argon gas, Krypton, xenon or nitrogen atmosphere.
The present invention also provides a kind of lithium ion battery negative material, and described negative material comprises negative active core-shell material, binding agent and conductive agent, and described negative active core-shell material is the negative active core-shell material that method of the present invention prepares.
In this negative material, binding agent is this area various materials commonly used, and for example described binding agent is selected from one or more in sodium carboxymethylcellulose, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, ethylene/propylene/diene hydrocarbon terpolymer, sulfonated EPDM, styrene/butadiene rubbers and the fluorubber.Preferred binding agent is the compound binding agent of styrene/butadiene rubbers and sodium carboxymethylcellulose.Described conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, the metal dust one or more.
In the above-mentioned negative material, the content of various materials is not too large restriction also, can adopt various relation with contents of the prior art, and for example the weight ratio of negative electrode active material, binding agent is 5-50:1, is preferably 10-35:1.Wherein, when adopting compound binding agent, the weight ratio of styrene/butadiene rubbers and sodium carboxymethylcellulose is 0.5-4:1.
The preparation method of this negative material is not particularly limited, and can directly negative electrode active material, binding agent and conductive agent be mixed to get final product.
Further, the effective utilization as above-mentioned negative material the invention also discloses a kind of lithium ion battery, comprises housing, is in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Described pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Described positive plate comprises positive collector and is coated in positive electrode on the positive collector; Described negative plate comprises negative collector and is coated in the negative material of bearing on the collector; Wherein, described negative material is negative material of the present invention.
The preparation method of above-mentioned lithium ion battery is commonly known in the art, for example positive and negative electrode active material, conductive agent and binding agent are dissolved in according to a certain percentage and are mixed into slurries in the solvent, apply these slurries at the wide cut conducting base again, then dry, roll-in is also cut, and obtains pole piece.
Condition dry and roll-in is known in those skilled in the art, and for example the temperature of dry negative plate is generally 60-120 ℃, and preferred 80-110 ℃, be 0.5-5 hour drying time.
The pole piece structure of battery provided by the present invention is this area pole piece structure commonly used, and in general, pole piece can adopt the mode of coiling or stacked positive plate, barrier film and negative plate to make, and coiling or stacked mode are that those skilled in the art are in common knowledge.
The present invention has no particular limits positive electrode material, and is the same with prior art, and positive electrode material generally includes positive active material, binding agent and conductive agent.Positive active material can adopt up to now can commercial all positive electrodes, such as LiFePO
4, Li
3V
2(PO4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F, LiFeO
2Deng, perhaps ternary system Li
1+xL
1-y-zM
yN
zO
2, wherein-and 0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0, L, M, N are at least a in Co, Mn, Ni, Al, Mg, Ga and the 3d transiting group metal elements.Binding agent can adopt any binding agent known in the field, for example can adopt in polyvinylidene fluoride, polytetrafluoroethylene or the butadiene-styrene rubber one or more.The content of binding agent is the 0.1-15wt% of described positive electrode, is preferably 1-7wt%.Conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.The content of described conductive agent is the 0.1-20wt% of described positive electrode, is preferably 2-10wt%.Anodal preparation method can adopt this area the whole bag of tricks commonly used, for example with solvent positive active material, binding agent and conductive agent are prepared into the positive electrode slurries, the addition of solvent is known in those skilled in the art, and the viscosity that can be coated with according to the slurry of anodal slurries to be prepared and the requirement of operability are adjusted flexibly.Then prepared positive electrode slurries slurry is coated in dry compressing tablet on the positive electrode collector, cut-parts obtain positive pole again.The temperature of described drying is generally 120 ℃, and be generally 5 hours drying time.The used solvent of anodal slurries can be various solvent of the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, it is the 40-90 % by weight that the consumption of solvent makes the content of positive active material in the slurries, is preferably the 50-85 % by weight.
The barrier film of battery of the present invention has electrical insulation capability and liquid retainability energy.Barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
The electrolyte of battery of the present invention is nonaqueous electrolytic solution.Nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol/L, is preferably the 0.8-1.2 mol/L.
The preparation method of battery of the present invention is well known for the person skilled in the art, and in general, the preparation method of this battery comprises pole piece is inserted in the battery case, adds electrolyte, and then sealing obtains battery.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
The present invention is further illustrated below by embodiment.
Embodiment 1
1, preparation negative active core-shell material
1.3g oleic acid and 1.69g NaOH are joined in the 30mL ethanol successively, be designated as A1 solution; With 3.24g FeCl
36H
2O is dissolved in the 75mL deionized water, is designated as B1 solution.B1 solution dropwise is added drop-wise in the A1 solution, behind the magnetic agitation 3h, changes in the teflon-lined reactor, 180 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively ethanol and deionized water supersound washing twice, remove residual oleic acid root and inorganic ions.Obtain presoma a1 after 60 ℃ of dryings, presoma a1 is changed in the tube furnace that is connected with argon gas stream, with 5 ℃ of min
-1Programming rate rise to 300 ℃ of insulation 1h, naturally lower the temperature, obtain sample b1.
2, preparation battery cathode
In mass ratio with negative active core-shell material: acetylene black: the ratio of SBR:CMC=80:10::6:4 mixes rear compressing tablet, and 120 ℃ of vacuumize 24h obtain cathode pole piece.
3, preparation lithium ion battery
Take metal lithium sheet as to electrode, the celgard2400 polypropylene porous film is barrier film, the mixed solution of the ethylene carbonate of 1mol/L LiPF6 (EC) and dimethyl carbonate (DMC) (be=1:1) assemble in being full of the glove box of argon gas for electrolyte, obtains battery sample c1 by volume ratio.
Embodiment 2
1.3g oleic acid and 1.69g NaOH are joined in the 30mL ethanol successively, be designated as A2 solution; With 3.24g FeCl
36H
2O is dissolved in the 75mL deionized water, is designated as B2 solution.B2 solution dropwise is added drop-wise in the A2 solution, behind the magnetic agitation 3h, changes in the teflon-lined reactor, 180 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively ethanol and deionized water supersound washing twice, remove residual oleic acid root and inorganic ions.Obtain presoma a2 after 60 ℃ of dryings, presoma a2 is changed in the tube furnace that is connected with argon gas stream, with 5 ℃ of min
-1Programming rate rise to 500 ℃ of insulation 1h, naturally lower the temperature, obtain sample b2.Method according to embodiment 1 prepares battery sample c2.
Embodiment 3
32.4g oleic acid and 8.1g NaOH are joined in the 30mL ethanol successively, be designated as A3 solution; With 3.24g FeCl
36H
2O is dissolved in the 75mL deionized water, is designated as B3 solution.B3 solution dropwise is added drop-wise in the A3 solution, behind the magnetic agitation 3h, changes in the teflon-lined reactor, 180 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively ethanol and deionized water supersound washing twice, remove residual oleic acid root and inorganic ions.Obtain presoma a3 after 60 ℃ of dryings, presoma a3 is changed in the tube furnace that is connected with argon gas stream, with 5 ℃ of min
-1Programming rate rise to 800 ℃ of insulation 1h, naturally lower the temperature, obtain sample b3.Method according to embodiment 1 prepares battery sample c3.
Example 4
1.3g diglycol and 2g ammoniacal liquor are joined in the 30mL ethanol successively, be designated as A4 solution; With 4g Fe (NO)
3Be dissolved in the 75mL deionized water, be designated as B4 solution.B4 solution dropwise is added drop-wise in the A4 solution, behind the magnetic agitation 2h, changes in the teflon-lined reactor, 200 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively twice of ethanol and deionized water supersound washing.Obtain presoma a4 after 80 ℃ of dryings, presoma a4 is changed in the tube furnace that is connected with argon gas stream, with 10 ℃ of min
-1Programming rate rise to respectively 800 ℃ of insulation 0.5h, naturally lower the temperature, obtain sample b4.Method according to embodiment 1 prepares battery sample c4.
Example 5
0.27g diglycol and 6.7g ammoniacal liquor are joined in the 30mL ethanol successively, be designated as A5 solution; With 4g Fe (NO)
3Be dissolved in the 75mL deionized water, be designated as B5 solution.B5 solution dropwise is added drop-wise in the A5 solution, behind the magnetic agitation 2h, changes in the teflon-lined reactor, 200 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively twice of ethanol and deionized water supersound washing.Obtain presoma a5 after 80 ℃ of dryings, presoma a5 is changed in the tube furnace that is connected with argon gas stream, with 10 ℃ of min
-1Programming rate rise to respectively 600 ℃ of insulation 0.5h, naturally lower the temperature, obtain sample b5.Method according to embodiment 1 prepares battery sample c5.
Example 6
1.58g acetonitrile and 1.8g KOH are joined in the 35mL acetone successively, be designated as A6 solution; With 3.24g Fe
2(SO4)
3Be dissolved in the 75mL deionized water, be designated as B6 solution.B6 solution dropwise is added drop-wise in the A6 solution, behind the magnetic agitation 5h, changes in the teflon-lined reactor, 100 ℃ of insulation 15h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively twice of ethanol and deionized water supersound washing.Obtain presoma a6 after 100 ℃ of dryings, presoma a6 is changed in the tube furnace that is connected with argon gas stream, with 15 ℃ of min
-1Programming rate rise to 500 ℃ of insulation 2h, naturally lower the temperature, obtain sample b6.Method according to embodiment 1 prepares battery sample c6.
Example 7
6.48g acetonitrile and 6.48g KOH are joined in the 35mL acetone successively, be designated as A7 solution; With 3.24g Fe
2(SO4)
3Be dissolved in the 75mL deionized water, be designated as B7 solution.B7 solution dropwise is added drop-wise in the A7 solution, behind the magnetic agitation 5h, changes in the teflon-lined reactor, 100 ℃ of insulation 15h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively twice of ethanol and deionized water supersound washing.Obtain presoma a7 after 100 ℃ of dryings, presoma a7 is changed in the tube furnace that is connected with argon gas stream, with 15 ℃ of min
-1Programming rate rise to 700 ℃ of insulation 2h, naturally lower the temperature, obtain sample b7.Method according to embodiment 1 prepares battery sample c7.
Embodiment 8
1.296g oleic acid and 4.05gNaOH are joined in the 30mL ethanol successively, be designated as A8 solution; With 3.24g FeCl
36H
2O is dissolved in the 75mL deionized water, is designated as B8 solution.B8 solution dropwise is added drop-wise in the A8 solution, behind the magnetic agitation 3h, changes in the teflon-lined reactor, 180 ℃ of insulation 10h.Naturally after the cooling, at the bottom of still, obtain bolarious presoma, use respectively ethanol and deionized water supersound washing twice, remove residual oleic acid root and inorganic ions.Obtain presoma a8 after 60 ℃ of dryings, presoma a8 is changed in the tube furnace that is connected with argon gas stream, rise to 600 ℃ of insulation 1h with the programming rate of 5 ℃ of min-1, naturally lower the temperature, obtain sample b8.Method according to embodiment 1 prepares battery sample c8.
Comparative Examples 1
Fe with the commerce purchase
3O
4(Hangzhou ten thousand scape new material Co., Ltds VK-EF03) as negative electrode active material, prepare battery sample Dc1 according to the method for embodiment 1.Negative active core-shell material is designated as Db1.
Comparative Examples 2
With 1.99 gram FeCl
24H
2O and 5.14 gram FeCl
36H
2O is dissolved in the 50 mL deionized waters, and add again 2 and restrain PEG-6000 and constantly stir the formation homogeneous solution, dropping 100 ml ammoniacal liquor in mentioned solution (25%, w/w), generate gradually black precipitate.After above-mentioned sediment filtration, use respectively ethanol and deionized water supersound washing twice, then after 60 ℃ of dryings, obtain Fe
3O
4/ C is designated as Db2.Method according to embodiment 1 prepares battery sample Dc2.
Performance test and sign
1, X-ray diffraction analysis
Employing Rigaku D/MAX-PC2200 X x ray diffractometer x (the Cu target, λ=0.15405nm)
Fig. 1 is respectively the XRD figure of sample a1 and b1, b2.Before the calcining, XRD peak and the α-Fe of sample
2O
3Base peak (JCPDS 33-0664) is consistent, but at 21 °, and 36.5 °, 53 ° and 59 ° of peaks of locating illustrate to have a small amount of alpha-feooh phase in the presoma corresponding to alpha-feooh (JCPDS 29-0713) diffraction maximum.Behind the lower 300 ℃ of heat treatment 1h of argon gas, shown in Fig. 1 (b), obtained α-Fe
2O
3With Fe
3O
4The mixing phase.Behind the lower 500 ℃ of heat treatment 1h of argon gas, the diffraction maximum of product (seeing Fig. 1 (c)) and Fe
3O
4(JCPDS 65-3107) is in full accord for base peak, shows the Fe that has obtained pure phase
3O
4Elementary analysis draws the lower 300 ℃ of 1h of argon gas and the 500 ℃ of heat treated sample difference of 1h carbon containings 2.356% and 1.956% (mass fraction).Therefore these two samples can be expressed as respectively α-Fe
2O
3/ Fe
3O
4/ C and Fe
3O
4/ C.The diffraction maximum that does not have corresponding carbon among the XRD figure illustrates that carbon is atypic.
2, Electronic Speculum
(SEM) tests sample a2 and b2 with ESEM.
Fig. 2 and 3 is respectively the SEM figure of sample a2 and b2.Presoma is spindle.The pattern of sample does not have significant change before and after the calcining, but the volume of particle has a little contraction after the calcining, is to be about 200nm, the spindle of thick approximately 100nm.Volume contraction and presoma α-Fe
2O
3Reduction obtains Fe
3O
4Relevant.500 ℃ of calcinings do not have agglomeration, and are main because the carbon on top layer as barrier layer, has stoped reunion.
3, chemical property
Battery sample c1-c8, Dc1 and Dc2 are carried out following performance test.
3.1 charging and discharging capacity
Battery is set to discharge condition, and discharge current density is 2mA/cm
2, discharge cut-off voltage is 5mV, discharge finishes namely out of service, calculates first discharge specific capacity, the results are shown in Table 1.
The quality of first discharge specific capacity (mAh/g)=first discharge capacity/active material
The quality of discharge capacity/active material after 5 circulation specific discharge capacities (mAh/g)=circulation discharge 5 times
After discharge finished first, battery was set to charged state again, and the density of charging current is 2mA/cm
2, charge cutoff voltage is 2.5V, charging finishes, and calculates the initial charge specific capacity.
The quality of initial charge specific capacity (mAh/g)=initial charge capacity/active material.
3.2 cycle performance
Constant current with 2mA carries out constant current charge to battery, charging is by voltage 2.5V, equally with the constant current of 2mA to the battery constant-current discharge, discharge cut-off voltage is 0.005V, shelves 10 minutes, repeats above step, make continuous charge-discharge test, obtain the battery capacity after battery circulates for 80 times, calculate the discharge capacitance of 80 rear batteries of circulation, test result is as shown in table 1.
Discharge capacity * 100% of discharge capacity after the circulation of discharge capacitance=80 time/first.
3.3 high rate performance
The capacity of specimen after circulation under 0.2C, 0.5C, C and the 2C 20 times respectively.The results are shown in Table 2.
Table 1
。
Table 2
As can be seen from Table 1, use Fe of the present invention
3O
4The first discharge specific capacity as the battery sample c1-c8 of battery cathode of/C electrode is not less than 1200 mAh/g, the battery sample Dc1 of Comparative Examples 1 and Comparative Examples 2 and the first discharge specific capacity of Dc2 are respectively 1362 mAh/g and 1182 mAh/g, and the part that exceeds theoretical specific capacity (928 mAh/g) mainly forms the SEI film from electrolyte decomposition.Use Fe of the present invention
3O
4/ C electrode as 5 circulation rear electrode capacity attenuations of the battery sample c1-c8 of battery cathode seldom, 5 later minimum 800mAh/g that still have, and the decay of the discharge capacity of the battery sample Dc1 of Comparative Examples 1 is serious, only has later on 595.5mAh/g 5 times, battery sample Dc2 the 5th of Comparative Examples 2 is filled only 620 mAh/g of specific capacitance, the Fe that also prepares far below method of the present invention
3O
4The 5th charge ratio capacity of/C.The Fe of method preparation of the present invention after 80 circulations
3O
480 cyclic discharge capacity conservation rates of/C electrode battery sample c1-c8 are more than 70%, and 80 cyclic discharge capacity conservation rates of the battery sample Dc1 of Comparative Examples 1 are 26.8%, and 80 cyclic discharge capacity conservation rates of the battery sample Dc2 of Comparative Examples 2 are 49.7%.
As can be seen from Table 2, along with the increase of discharge-rate, the battery sample Dc1 decay of the specific discharge capacity Comparative Examples 1 after 20 times that circulates is the most serious, and the battery sample Dc2 of Comparative Examples 2 and battery sample c1-c8 of the present invention are similar to.Under 2C, battery sample c1-c8 of the present invention is minimum in the later specific capacity of 20 circulations to be 520 mAh/g, and Comparative Examples 1 only has 110 mAh/g, and Comparative Examples 2 is 405 mAh/g.Downward trend is similar with the multiplying power increase for the specific discharge capacity of the battery sample in battery sample c1-c8 of the present invention and the Comparative Examples 2, the two under the 2C multiplying power specific capacity all above the graphite theoretical capacity, be better than equally Comparative Examples 1, but the specific capacity of the battery sample of battery sample of the present invention comparison Comparative Examples 2 has promoted approximately 30%.
Claims (13)
1. lithium ion battery anode active material Fe
3O
4The preparation method of/C is characterized in that, the method may further comprise the steps:
S1, surfactant, precipitation reagent joined be mixed into solution A in the organic solvent;
S2, with solvable trivalent metal iron salt dissolved wiring solution-forming B in water;
S3, solution B slowly is added in the solution A, then changes in the reactor, naturally cool off after 10-15 hour 100-200 ℃ of insulation, obtain presoma;
S4, remove the impurity that remains in the presoma surface, dry after under inert atmosphere, with 5-15 ℃ of min
-1Speed be warming up to 300-800 ℃ of insulation 0.5-2 hour, naturally lower the temperature, obtain negative active core-shell material;
Wherein precipitation reagent is the material that can form with iron ion precipitation.
2. preparation method according to claim 1 is characterized in that, described surfactant is that the carbon number of the carbochain between hydrophilic radical and the lipophilic group is the surfactant of 3-18.
3. preparation method according to claim 2 is characterized in that, described surfactant is oleic acid, at least a in acetonitrile, salicylic acid, diglycol, glycerine, glucose, sucrose and the sodium cetanesulfonate.
4. preparation method according to claim 1 is characterized in that, described precipitation reagent is soluble hydroxide or ammoniacal liquor.
5. preparation method according to claim 1 is characterized in that, described soluble metal molysite is FeCl
36H
2O, Fe (NO)
3And Fe
2(SO4)
3In at least a.
6. preparation method according to claim 1 is characterized in that, what described organic solvent can be in ethanol, acetone, acetic acid, ethylene glycol, chloroform, oxolane and the naphthalene is at least a.
7. preparation method according to claim 1 is characterized in that, the mass ratio of described surfactant, precipitation reagent and metal molysite is 1:0.25-25:0.1-15.
8. preparation method according to claim 1 is characterized in that, the mass ratio of described surfactant, precipitation reagent and metal molysite is 1:1-3.125:0.5-2.5.
9. preparation method according to claim 1 is characterized in that, described method stirs its mixture after also being included in and slowly being added to solution B in the solution A, and the time of described stirring is 2-5 hour.
10. preparation method according to claim 1 is characterized in that, the baking temperature among the described step S4 is 60-100 ℃.
11. preparation method according to claim 1 is characterized in that, described inert atmosphere is helium, neon, argon gas, Krypton, xenon or nitrogen atmosphere.
12. a lithium ion battery negative material, described negative material comprises negative active core-shell material, binding agent and conductive agent, it is characterized in that, described negative active core-shell material is the negative active core-shell material that the described method of claim 1-11 any one prepares.
13. a lithium ion battery comprises housing, is in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Described pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Described positive plate comprises positive collector and is coated in positive electrode on the positive collector; Described negative plate comprises negative collector and is coated in the negative material of bearing on the collector; It is characterized in that, described negative material is the described negative material of claim 12.
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Cited By (6)
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| CN104045116A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material |
| CN104241645A (en) * | 2014-04-29 | 2014-12-24 | 常州普格纳能源材料有限公司 | Synthesis method of lithium-manganese-phosphate anode material |
| CN108306001A (en) * | 2018-01-08 | 2018-07-20 | 北京科技大学 | Lithium ion battery negative material Fe3O4The preparation method of/N-C |
| CN108428877A (en) * | 2018-03-28 | 2018-08-21 | 成都理工大学 | Nanometer Fe3O4@C In-situ reaction porous lithium ion cell negative materials and preparation method thereof |
| CN109244381A (en) * | 2018-07-24 | 2019-01-18 | 昆明理工大学 | A kind of preparation method of carbon coated ferriferrous oxide nanosphere |
| CN109950523A (en) * | 2019-03-14 | 2019-06-28 | 常熟理工学院 | Lithium ion battery negative material transition metal oxide/carbon preparation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241645A (en) * | 2014-04-29 | 2014-12-24 | 常州普格纳能源材料有限公司 | Synthesis method of lithium-manganese-phosphate anode material |
| CN104045116A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material |
| CN104045116B (en) * | 2014-06-12 | 2016-01-27 | 江苏大学 | The preparation method of nano porous metal oxide/carbon lithium ion battery negative material |
| CN108306001A (en) * | 2018-01-08 | 2018-07-20 | 北京科技大学 | Lithium ion battery negative material Fe3O4The preparation method of/N-C |
| CN108306001B (en) * | 2018-01-08 | 2021-04-16 | 北京科技大学 | Lithium ion battery cathode material Fe3O4Preparation method of/N-C |
| CN108428877A (en) * | 2018-03-28 | 2018-08-21 | 成都理工大学 | Nanometer Fe3O4@C In-situ reaction porous lithium ion cell negative materials and preparation method thereof |
| CN109244381A (en) * | 2018-07-24 | 2019-01-18 | 昆明理工大学 | A kind of preparation method of carbon coated ferriferrous oxide nanosphere |
| CN109950523A (en) * | 2019-03-14 | 2019-06-28 | 常熟理工学院 | Lithium ion battery negative material transition metal oxide/carbon preparation method |
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